electronic structure and bonding of lanthanoid(iii) carbonates. · 2012-08-01 · electronic...

27
Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine, a Pere Miró, b Fausto Martelli, a Christopher J. Cramer b,* and Riccardo Spezia a,* a Université d’Evry Val d’Essonne, CNRS UMR 8587 LAMBE, Bd F. Mitterrand, 91025 Evry Cedex, France. b Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 USA. SUPPORTING INFORMATION Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics This journal is © The Owner Societies 2012

Upload: others

Post on 04-Jun-2020

5 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b Fausto Martelli,a Christopher J. Cramerb,* and Riccardo Speziaa,*

aUniversité d’Evry Val d’Essonne, CNRS UMR 8587 LAMBE, Bd F. Mitterrand, 91025 Evry Cedex, France.

bDepartment of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455-0431 USA.

 

SUPPORTING INFORMATION

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 2: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

 

Contents      Figure S1. La3+-CO3

2- energy curves for various basis set. Basis1 = 6-31+G(d,p); basis 2 = 6-311+G(d,p) ; basis 3 = 6-311++G(3df,2p) ; basis 4 = AUG-cc-pVTZ.

Table S1.  Distances (in Å) between Ln, oxygen and carbon atoms in optimized geometries. O(1) is/are the oxygen(s) closer to Ln, O(2) the farest one(s).  

Table S2. Energy decomposition analysis (EDA) in gas phase of the La-ligand interation. The metal centre (M3+) was chosen as a fragment and the three/four ligands ({CO3

2-}3/4) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S3. Energy decomposition analysis (EDA) in gas phase of the Lu-ligand interation. The metal centre (M3+) was chosen as a fragment and the three/four ligands ({CO3

2-}3/4) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S4. Energy decomposition analysis (EDA) in gas phase of the La-ligand interation. The metal centre with 3 carbonates ({M(CO3

2-)2}-1) was chosen as a fragment and the remaining ligand (CO3

2-) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S5. Energy decomposition analysis (EDA) in gas phase of the Lu-ligand interation. The metal centre with 3 carbonates ({M(CO3

2-)2}-1) was chosen as a fragment and the remaining ligand (CO3

2-) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S6. Natural Orbitals for Chemical Valence in gas phase for in the fragments presented in Table 3 in La species with 3 carbonate ligands. Energy in kcal·mol-1 (only energies above 5kcal·mol-1 are presented). The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S7. Natural Orbitals for Chemical Valence in gas phase for in the fragments presented in Table 4 in Lu species with 3 carbonate ligands. Energy in kcal·mol-1 (only energies above 5kcal·mol-1 are presented). The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

Table S8. Topological analysis of the electron density of La species with 3 carbonate ligands. Gas phase calculations.

Table S9. Topological analysis of the electron density of La species with 4 carbonate ligands. Gas phase calculations.

Table S10. Topological analysis of the electron density of Lu species with 3 carbonate ligands. Gas phase calculations.

Table S11. Topological analysis of the electron density of Lu species with 4 carbonate ligands. Gas phase calculations.

Table S12. Cartesian coordinates of La species with 3 carbonate ligands.

Table S13. Cartesian coordinates of La species with 4 carbonate ligands.

Table S14. Cartesian coordinates of Lu species with 3 carbonate ligands.

Table S15. Cartesian coordinates of Lu species with 4 carbonate ligands.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 3: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S16. Second-order perturbative estimates of donor-acceptor interactions in the NBO basis between carbonates and Ln(III). We specify the character of the acceptor orbital, while for the donor it always correspond to oxygen lone pair. Only energies above 10 kcal mol-1 are reported.

Table S17. Relative energy obtained with different functionals with B3LYP optimized geometries (fixed) and optimizing the geometry with the given functional. Energies are in kcal/mol.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 4: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Figure S1. La3+-CO32- energy curves for various basis set. Basis1 = 6-31+G(d,p); basis 2 = 6-

311+G(d,p) ; basis 3 = 6-311++G(3df,2p) ; basis 4 = AUG-cc-pVTZ.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 5: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S1.  Distances (in Å) between Ln, oxygen and carbon atoms in optimized geometries. O(1) is/are the oxygen(s) closer to Ln, O(2) the farest one(s). The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).

 

Ln-O(1) Ln-O(2) Ln-C LaC3 3m 2.20 4.29 3.60

2m1b 2.23/2.41 4.33/4.12 3.61/2.87 1m2b 2.44/2.25 4.16/4.36 2.90/3.62

3b 2.47 4.19 2.93  

LaC4 4m 2.34 4.49 3.7

3m1b 2.38/2.60 4.49/4.30 3.72/3.01 2m2b 2.43/2.55 4.53/4.33 3.72/3.01 1m3b 2.59/2.47 4.58/4.38 3.81/3.09

4b 2.64 4.42 3.12  

LuC3 3m 2.02 4.13 3.41

2m1b 2.04/2.20 4.15/3.89 2.64/3.42 1m2b 2.24/2.06 3.94/4.16 3.43/2.68

3b 2.27 3.97 2.71  

LuC4 4m 2.13 4.21 3.48

3m1b 2.18/2.29 4.31/4.08 3.50/2.80 2m2b 2.21/2.43 4.31/4.10 3.54/2.82 1m3b 2.24/2.49 4.35/4.13 3.57/2.87

4b 2.48 4.2 2.9  

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 6: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S2. Energy decomposition analysis (EDA) in gas phase of the La-ligand interation. The metal centre (M3+) was chosen as a fragment and the three/four ligands ({CO3

2-}3/4) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).  

Species Pauli Repulsion Orbitalic Interaction

Electrostatic Interaction

3m 245.64 -344.33 (16.01%) -1806.09 (84.99%) 2m1b 246.32 -329.93 (14.99%) -1871.09 (85.01%) 1m2b 241.29 -314.75 (14.02%) -1930.34 (85.98%)

3b 232.89 -299.36 (13.10%) -1985.49 (86.90%)

4m 177.67 -337.96 (12.48%) -2168.35 (86.52%) 3m1b 170.61 -323.56 (12.74%) -2216.42 (87.26%) 2m2b 163.60 -309.65 (12.03%) -2264.64 (87.97%) 1m3b 155.16 -297.99 (11.43%) -2308.89 (88.57%)

4b 145.29 -286.47 (10.86%) -2350.77 (89.14%)                                                                    

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 7: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S3. Energy decomposition analysis (EDA) in gas phase of the Lu-ligand interation. The metal centre (M3+) was chosen as a fragment and the three/four ligands ({CO3

2-}3/4) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).  

Species Pauli Repulsion Orbitalic Interaction

Electrostatic Interaction

3m 237.37 -384.53 (16.88%) -1892.91 (83.12%) 2m1b 244.41 -377.15 (16.07%) -1969.96 (83.93%) 1m2b 238.74 -365.01 (15.21%) -2034.24 (84.79%)

3b 229.29 -350.53 (14.34%) -2094.31 (85.66%)

4m 181.19 -402.95 (15.06%) -2272.17 (84.94%) 3m1b 171.83 -387.51 (14.30%) -2322.35 (85.70%) 2m2b 163.95 -373.40 (13.59%) -2374.79 (86.41%) 1m3b 153.19 -361.52 (13.00%) -2420.44 (87.00%)

4b 141.33 -348.76 (12.40%) -2464.02 (87.60%)                                                                      

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 8: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S4. Energy decomposition analysis (EDA) in gas phase of the La-ligand interation. The metal centre with 3 carbonates ({M(CO3

2-)2}-1) was chosen as a fragment and the remaining ligand (CO3

2-) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).  

Species Ligand Pauli Repulsion

Orbitalic Interaction

Electrostatic Interaction

3m mo 114.53 -90.10 (47.54%) -99.41 (52.46%) 2m1b mo 104.40 -81.04 (50.61%) -79.10 (49.39%) 2m1b bi 130.23 -95.94 (42.33%) -130.71 (57.67%) 1m2b mo 95.05 -73.77 (55.78%) -58.48 (44.22%) 1m2b bi 116.49 -85.67 (45.08%) -104.36 (54.92%)

3b bi 104.37 -77.73 (49.80%) -78.36 (50.20%)                                                                            

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 9: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S5. Energy decomposition analysis (EDA) in gas phase of the Lu-ligand interation. The metal centre with 3 carbonates ({M(CO3

2-)2}-1) was chosen as a fragment and the remaining ligand (CO3

2-) as the other fragment. Energies in kcal·mol-1. The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b).  

Species Ligand Pauli Repulsion

Orbitalic Interaction

Electrostatic Interaction

3m m 126.26 -101.25 (46.63%) -115.89 (53.37%) 2m1b m 106.18 -79.47 (45.87%) -93.79 (54.13%) 2m1b b 149.5 -104.4 (38.83%) -164.3 (54.13%) 1m2b m 97.14 -72.11 (50.61%) -70.38 (49.39%) 1m2b b 125.03 -87.78 (41.23%) -125.13 (58.77%)

3b b 111.87 -78.96 (45.97%) -92.80 (54.03%)                                                                            

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 10: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

 Table S6. Natural Orbitals for Chemical Valence in gas phase for in the fragments presented in Table 3 in La species with 3 carbonate ligands. Energy in kcal·mol-1 (only energies above 5kcal·mol-1 are presented). The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b). Energies are highly dependent on the fragment choice.      

                                                     

Species Ligand Orbitals Energy 3m m 1st O-2p → La-5d0 -24.29959

2nd O-2p → La-5d0 -31.35437 3rd O-2p → La-5d0 -15.06170

2m1b m 1st O-2p → La-5d0 -20.31610 2nd O-2p → La-5d0 -29.32818 3rd O-2p → La-5d0 -13.83859

2m1b b 1st O-2p → La-5d0 -35.16901 2nd O-2p → La-5d0 -21.51368 3rd O-2p → La-5d0 -8.31394

1m2b m 1st O-2p → La-5d0 -27.11360 2nd O-2p → La-5d0 -17.50859 3rd O-2p → La-5d0 -12.70027

1m2b b 1st O-2p → La-5d0 -30.21364 2nd O-2p → La-5d0 -20.60048 3rd O-2p → La-5d0 -7.30717

3b b 1st O-2p → La-5d0 -26.75174 2nd O-2p → La-5d0 -19.45519 3rd O-2p → La-5d0 -6.47782

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 11: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S7. Natural Orbitals for Chemical Valence in gas phase for in the fragments presented in Table 4 in Lu species with 3 carbonate ligands. Energy in kcal·mol-1 (only energies above 5kcal·mol-1 are presented). The carbonate coordination motifs are designated as number monodentate (m) or bidentate (b). Energies are highly dependent on the fragment choice.      

* Inside fragment 1 with really small contribution of fragment 2.                                                

Species Ligand Orbitals Energy 3m m 1st O-2p → Lu-6s -14.62685*

2nd O-2p → Lu-5d0 -21.20628 3rd O-2p → Lu-5d0 -18.35011 4th O-2p → Lu-5d0 -13.93904

2m1b m 1st O-2p → Lu-5d0 -17.35802 2nd O-2p → Lu-5d0 -22.82156 3rd O-2p → Lu-5d0 -14.95281

2m1b b 1st O-2p → Lu-5d0 -17.24372 2nd O-2p → Lu-5d0 -22.93462 3rd O-2p → Lu-5d0 -14.96220

1m2b m 1st O-2p → Lu-5d0 -14.70391 2nd O-2p → Lu-5d0 -21.94559 3rd O-2p → Lu-5d0 -12.28322

1m2b b 1st O-2p → Lu-5d0 -25.80296 2nd O-2p → Lu-5d0 -20.22867 3rd O-2p → Lu-5d0 -7.07274

3b b 1st O-2p → Lu-5d0 -23.02938 2nd O-2p → Lu-5d0 -17.82575 3rd O-2p → Lu-5d0 -6.38278

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 12: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S8. Topological analysis of the electron density of La species with 3 carbonate ligands. Gas phase calculations.  

LaCar3_0bi3mo   Type ρb   ∇2ρb   Gb Gb/ρb   Vb Ee

b La-Ocarb (3,-1) 0.0838 0.4091 0.1024 1.2224 -0.1025 -0.0001 La-Ocarb (3,-1) 0.0839 0.4090 0.1026 1.2235 -0.1030 -0.0003 La-Ocarb (3,-1) 0.0837 0.3987 0.1023 1.2219 -0.1049 -0.0026

 

 LaCar3_2bi1mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  La-Ocarb (3,-1) 0.0755 0.3710 0.0911 1.2066 -0.0895 0.0016 La-Ocarb' (3,-1) 0.0579 0.2267 0.0541 0.9344 -0.0515 0.0026 La-Ocarb' (3,-1) 0.0577 0.2264 0.0540 0.9359 -0.0514 0.0026 La-Ocarb' (3,-1) 0.0579 0.2269 0.0541 0.9344 -0.0515 0.0026 La-Ocarb' (3,-1) 0.0579 0.2268 0.0541 0.9344 -0.0515 0.0026

La-(Ocarb)2 (3,+1) 0.0326 0.1753 0.0398 1.2209 -0.0358 0.0040 La-(Ocarb)2 (3,+1) 0.0327 0.1756 0.0399 1.2202 -0.0359 0.0040

 LaCar3_3bi0mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  La-Ocarb' (3,-1) 0.0542 0.2121 0.0501 0.9243 -0.0472 0.0029 La-Ocarb' (3,-1) 0.0542 0.2120 0.0501 0.9243 -0.0472 0.0029 La-Ocarb' (3,-1) 0.0541 0.2131 0.0500 0.9242 -0.0467 0.0033 La-Ocarb' (3,-1) 0.0543 0.2139 0.0502 0.9245 -0.0470 0.0033 La-Ocarb' (3,-1) 0.0542 0.2134 0.0501 0.9243 -0.0468 0.0033 La-Ocarb' (3,-1) 0.0542 0.2135 0.0501 0.9245 -0.0468 0.0033

La-(Ocarb)2 (3,+1) 0.0312 0.1633 0.0373 1.1946 -0.0337 0.0035 La-(Ocarb)2 (3,+1) 0.0312 0.1643 0.0374 1.1984 -0.0335 0.0039 La-(Ocarb)2 (3,+1) 0.0312 0.1653 0.0373 1.1949 -0.0332 0.0041

                       

LaCar3_1bi2mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

La-Ocarb (3,-1) 0.0794 0.3887 0.0964 1.2148 -0.0957 0.0008 La-Ocarb (3,-1) 0.0794 0.3887 0.0964 1.2148 -0.0957 0.0008 La-Ocarb' (3,-1) 0.0620 0.2395 0.0586 0.9453 -0.0574 0.0012 La-Ocarb' (3,-1) 0.0620 0.2395 0.0586 0.9453 -0.0574 0.0012

La-(Ocarb)2 (3,+1) 0.0343 0.1844 0.0427 1.2460 -0.0393 0.0034

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 13: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S9. Topological analysis of the electron density of La species with 4 carbonate ligands. Gas phase calculations.  

LaCar4_0bi4mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

La-Ocarb (3,-1) 0.0603 0.3058 0.0699 1.1588 -0.0633 0.0066 La-Ocarb (3,-1) 0.0602 0.3056 0.0698 1.1595 -0.0632 0.0066 La-Ocarb (3,-1) 0.0603 0.3058 0.0699 1.1585 -0.0633 0.0066 La-Ocarb (3,-1) 0.0604 0.3061 0.0699 1.1585 -0.0634 0.0066

 LaCar4_1bi3mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  La-Ocarb (3,-1) 0.0546 0.2746 0.0621 1.1378 -0.0555 0.0066 La-Ocarb (3,-1) 0.0560 0.2843 0.0639 1.1411 -0.0567 0.0072 La-Ocarb (3,-1) 0.0560 0.2843 0.0639 1.1411 -0.0567 0.0072 La-Ocarb (3,-1) 0.0493 0.1599 0.0443 0.8995 -0.0487 -0.0043 La-Ocarb (3,-1) 0.0405 0.1601 0.0357 0.8809 -0.0313 0.0044

La-(Ocarb)2 (3,+1) 0.0272 0.1349 0.0306 1.1215 -0.0274 0.0032  

LaCar4_2bi2mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

La-Ocarb (3,-1) 0.0499 0.2527 0.0557 1.1182 -0.0483 0.0074 La-Ocarb (3,-1) 0.0499 0.2527 0.0557 1.1182 -0.0483 0.0074 La-Ocarb (3,-1) 0.0458 0.1783 0.0406 0.8858 -0.0366 0.0040 La-Ocarb (3,-1) 0.0386 0.1528 0.0336 0.8713 -0.0290 0.0046 La-Ocarb (3,-1) 0.0458 0.1783 0.0406 0.8858 -0.0366 0.0040 La-Ocarb (3,-1) 0.0386 0.1528 0.0336 0.8713 -0.0290 0.0046

La-(Ocarb)2 (3,+1) 0.0259 0.1328 0.0286 1.1042 -0.0240 0.0046 La-(Ocarb)2 (3,+1) 0.0259 0.1328 0.0286 1.1042 -0.0240 0.0046

 LaCar4_3bi1mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  La-Ocarb (3,-1) 0.0339 0.1325 0.0289 0.8514 -0.0246 0.0043 La-Ocarb (3,-1) 0.0420 0.1619 0.0366 0.8696 -0.0326 0.0039 La-Ocarb (3,-1) 0.0379 0.1490 0.0328 0.8658 -0.0284 0.0044 La-Ocarb (3,-1) 0.0416 0.1522 0.0363 0.8706 -0.0345 0.0018 La-Ocarb (3,-1) 0.0420 0.1619 0.0366 0.8698 -0.0326 0.0039 La-Ocarb (3,-1) 0.0340 0.1329 0.0290 0.8516 -0.0247 0.0043 La-Ocarb (3,-1) 0.0447 0.2264 0.0490 1.0968 -0.0413 0.0076

La-(Ocarb)2 (3,+1) 0.0238 0.1173 0.0256 1.0726 -0.0218 0.0038 La-(Ocarb)2 (3,+1) 0.0248 0.1239 0.0270 1.0908 -0.0231 0.0039 La-(Ocarb)2 (3,+1) 0.0239 0.1175 0.0256 1.0733 -0.0218 0.0038

                 

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 14: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

 LaCar4_4bi0mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  La-Ocarb (3,-1) 0.0327 0.1284 0.0276 0.8435 -0.0230 0.0046 La-Ocarb (3,-1) 0.0372 0.1438 0.0317 0.8518 -0.0274 0.0043 La-Ocarb (3,-1) 0.0327 0.1288 0.0276 0.8433 -0.0229 0.0047 La-Ocarb (3,-1) 0.0371 0.1436 0.0316 0.8516 -0.0274 0.0043 La-Ocarb (3,-1) 0.0371 0.1436 0.0316 0.8519 -0.0274 0.0043 La-Ocarb (3,-1) 0.0327 0.1291 0.0276 0.8436 -0.0230 0.0047 La-Ocarb (3,-1) 0.0327 0.1285 0.0276 0.8434 -0.0230 0.0046 La-Ocarb (3,-1) 0.0372 0.1437 0.0317 0.8518 -0.0274 0.0043

La-(Ocarb)2 (3,+1) 0.0224 0.1096 0.0236 1.0508 -0.0197 0.0038 La-(Ocarb)2 (3,+1) 0.0224 0.1096 0.0236 1.0508 -0.0197 0.0039 La-(Ocarb)2 (3,+1) 0.0224 0.1098 0.0236 1.0512 -0.0197 0.0039 La-(Ocarb)2 (3,+1) 0.0224 0.1096 0.0236 1.0513 -0.0198 0.0038

                                                                       

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 15: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S10. Topological analysis of the electron density of Lu species with 3 carbonate ligands. Gas phase calculations.  

LuCar3_0bi3mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.1011 0.6453 0.1613 1.5955 -0.1613 0.0000 Lu-Ocarb (3,-1) 0.1012 0.6438 0.1614 1.5949 -0.1619 -0.0005 Lu-Ocarb (3,-1) 0.1012 0.6394 0.1614 1.5949 -0.1630 -0.0016  

LuCar3_1bi2mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0957 0.6069 0.1505 1.5720 -0.1493 0.0012 Lu-Ocarb (3,-1) 0.0958 0.6069 0.1506 1.5725 -0.1495 0.0011 Lu-Ocarb (3,-1) 0.0754 0.3852 0.0954 1.2643 -0.0945 0.0009 Lu-Ocarb (3,-1) 0.0754 0.3851 0.0954 1.2644 -0.0944 0.0009

Lu-(Ocarb)2 (3,+1) 0.0408 0.2427 0.0576 1.4112 -0.0544 0.0031  

LuCar3_2bi1mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0923 0.5851 0.1437 1.5572 -0.1411 0.0026 Lu-Ocarb (3,-1) 0.0684 0.3484 0.0844 1.2336 -0.0817 0.0027 Lu-Ocarb (3,-1) 0.0685 0.3489 0.0845 1.2339 -0.0818 0.0027 Lu-Ocarb (3,-1) 0.0685 0.3487 0.0845 1.2337 -0.0817 0.0027 Lu-Ocarb (3,-1) 0.0684 0.3485 0.0844 1.2337 -0.0817 0.0027

Lu-(Ocarb)2 (3,+1) 0.0383 0.2242 0.0526 1.3726 -0.0491 0.0035 Lu-(Ocarb)2 (3,+1) 0.0383 0.2242 0.0526 1.3727 -0.0491 0.0035  

LuCar3_3bi0mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0638 0.3193 0.0771 1.2089 -0.0744 0.0027 Lu-Ocarb (3,-1) 0.0638 0.3189 0.0771 1.2086 -0.0744 0.0027 Lu-Ocarb (3,-1) 0.0638 0.3242 0.0771 1.2088 -0.0732 0.0040 Lu-Ocarb (3,-1) 0.0637 0.3246 0.0771 1.2088 -0.0729 0.0041 Lu-Ocarb (3,-1) 0.0638 0.3248 0.0771 1.2089 -0.0730 0.0041 Lu-Ocarb (3,-1) 0.0638 0.3240 0.0771 1.2088 -0.0731 0.0039

Lu-(Ocarb)2 (3,+1) 0.0365 0.2140 0.0490 1.3418 -0.0444 0.0046 Lu-(Ocarb)2 (3,+1) 0.0365 0.2134 0.0490 1.3421 -0.0446 0.0044 Lu-(Ocarb)2 (3,+1) 0.0365 0.2049 0.0490 1.3421 -0.0467 0.0023                        

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 16: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S11. Topological analysis of the electron density of Lu species with 4 carbonate ligands. Gas phase calculations.  

LuCar4_0bi4mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0759 0.4778 0.1115 1.4692 -0.1036 0.0079 Lu-Ocarb (3,-1) 0.0758 0.4779 0.1115 1.4704 -0.1035 0.0080 Lu-Ocarb (3,-1) 0.0758 0.4767 0.1113 1.4687 -0.1034 0.0079 Lu-Ocarb (3,-1) 0.0758 0.4770 0.1113 1.4685 -0.1033 0.0080

 LuCar4_1bi3mo

  Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  Lu-Ocarb (3,-1) 0.0682 0.4202 0.0974 1.4279 -0.0898 0.0076 Lu-Ocarb (3,-1) 0.0606 0.2079 0.0722 1.1914 -0.0923 -0.0202 Lu-Ocarb (3,-1) 0.0449 0.2257 0.0509 1.1343 -0.0455 0.0055 Lu-Ocarb (3,-1) 0.0705 0.4470 0.1019 1.4454 -0.0921 0.0098 Lu-Ocarb (3,-1) 0.0705 0.4472 0.1019 1.4456 -0.0920 0.0099

Lu-(Ocarb)2 (3,+1) 0.0319 0.1724 0.0401 1.2586 -0.0371 0.0030  

LuCar4_2bi2mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0631 0.3743 0.0885 1.4020 -0.0834 0.0051 Lu-Ocarb (3,-1) 0.0436 0.2071 0.0488 1.1194 -0.0458 0.0030 Lu-Ocarb (3,-1) 0.0556 0.2348 0.0643 1.1571 -0.0699 -0.0056 Lu-Ocarb (3,-1) 0.0631 0.3743 0.0885 1.4020 -0.0834 0.0051 Lu-Ocarb (3,-1) 0.0436 0.2071 0.0488 1.1194 -0.0457 0.0030 Lu-Ocarb (3,-1) 0.0556 0.2348 0.0643 1.1569 -0.0699 -0.0056

Lu-(Ocarb)2 (3,+1) 0.0304 0.1696 0.0377 1.2411 -0.0331 0.0047 Lu-(Ocarb)2 (3,+1) 0.0304 0.1696 0.0377 1.2408 -0.0330 0.0047  

LuCar4_3bi1mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0381 0.1817 0.0409 1.0730 -0.0364 0.0045 Lu-Ocarb (3,-1) 0.0502 0.2330 0.0565 1.1257 -0.0548 0.0017 Lu-Ocarb (3,-1) 0.0451 0.2196 0.0502 1.1145 -0.0455 0.0047 Lu-Ocarb (3,-1) 0.0381 0.1817 0.0409 1.0729 -0.0364 0.0045 Lu-Ocarb (3,-1) 0.0574 0.3557 0.0788 1.3710 -0.0686 0.0102 Lu-Ocarb (3,-1) 0.0484 0.2097 0.0542 1.1200 -0.0560 -0.0018 Lu-Ocarb (3,-1) 0.0502 0.2330 0.0565 1.1257 -0.0548 0.0017

Lu-(Ocarb)2 (3,+1) 0.0279 0.1513 0.0334 1.1948 -0.0289 0.0045 Lu-(Ocarb)2 (3,+1) 0.0279 0.1512 0.0334 1.1948 -0.0289 0.0045 Lu-(Ocarb)2 (3,+1) 0.0292 0.1619 0.0360 1.2299 -0.0314 0.0045                  

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 17: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

LuCar4_4bi0mo   Type   ρb   ∇2ρb   Gb   Gb/ρb   Vb   Eeb  

Lu-Ocarb (3,-1) 0.0424 0.2025 0.0459 1.0838 -0.0412 0.0047 Lu-Ocarb (3,-1) 0.0392 0.1775 0.0418 1.0661 -0.0392 0.0026 Lu-Ocarb (3,-1) 0.0392 0.1775 0.0418 1.0658 -0.0392 0.0026 Lu-Ocarb (3,-1) 0.0422 0.2018 0.0457 1.0831 -0.0410 0.0047 Lu-Ocarb (3,-1) 0.0422 0.2016 0.0457 1.0830 -0.0410 0.0047 Lu-Ocarb (3,-1) 0.0392 0.1776 0.0418 1.0661 -0.0392 0.0026 Lu-Ocarb (3,-1) 0.0390 0.1767 0.0416 1.0651 -0.0389 0.0026 Lu-Ocarb (3,-1) 0.0422 0.2018 0.0457 1.0829 -0.0410 0.0047

Lu-(Ocarb)2 (3,+1) 0.0266 0.1383 0.0312 1.1722 -0.0278 0.0034 Lu-(Ocarb)2 (3,+1) 0.0266 0.1381 0.0311 1.1716 -0.0277 0.0034 Lu-(Ocarb)2 (3,+1) 0.0266 0.1381 0.0311 1.1716 -0.0277 0.0034 Lu-(Ocarb)2 (3,+1) 0.0265 0.1378 0.0311 1.1711 -0.0277 0.0034                                                                          

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 18: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

 Table S12. Cartesian coordinates of La species with 3 carbonate ligands.  

LaCar3_0bi3mo La -0.001100 -0.001317 -0.003841 C 0.979727 3.460611 0.003216 O 0.598942 2.120032 -0.019993 O -2.138067 -0.541039 0.000191 C -3.488988 -0.882287 0.002871 O -4.029372 -1.017313 1.140121 O 1.534870 -1.582998 -0.039540 C 2.511531 -2.575103 0.003984 O 2.929735 -2.999922 -1.113025 O 1.133407 4.018540 -1.122739 O 1.131726 3.978245 1.148888 O -4.033327 -1.021122 -1.131908 O 2.878225 -2.947456 1.157820

LaCar3_1bi2mo

La -0.000008 0.142728 -0.000170 C -3.136147 -1.645988 0.000316 O -3.630973 -1.921231 1.136948 O -3.635757 -1.925052 -1.133273 O -1.927668 -0.969971 -0.003309 O 0.001160 2.283239 -1.116700 C 0.000883 3.011529 -0.000064 O 0.000127 2.283125 1.116595 O 1.927113 -0.970722 0.003121 C 3.135285 -1.647303 0.000088 O 3.629700 -1.924258 -1.136323 O 3.635051 -1.925137 1.133887 O 0.001290 4.264391 0.000010

LaCar3_2bi1mo

La 0.152569 -0.000095 0.000359 C -3.470357 -0.012056 -0.000357 C 1.597478 -2.515003 -0.000306 C 1.573539 2.527740 0.000293 O -4.042988 -0.015288 1.136622 O -2.092720 -0.012015 -0.006612 O -4.053353 -0.009669 -1.132067 O 2.233334 -3.600764 -0.001370 O 1.230775 -1.890853 1.114971 O 1.234375 -1.887309 -1.114875 O 2.199971 3.618833 0.000186 O 1.215358 1.897674 -1.114429 O 1.212701 1.899554 1.115297

LaCar3_3bi0mo

La -0.000012 -0.000657 -0.000988 C -0.026028 2.928162 0.001077 C -2.524303 -1.485849 -0.000184

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 19: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

C 2.550304 -1.441060 0.001157 O -0.035387 4.191379 0.001967 O -0.015864 2.207972 -1.113003 O -0.025084 2.206473 1.114245 O -3.614594 -2.123842 -0.000995 O -1.902533 -1.122054 1.113570 O -1.901802 -1.120938 -1.113697 O 3.650856 -2.061203 0.001922 O 1.919973 -1.089748 1.114375 O 1.924542 -1.084294 -1.112883

                                                                                 

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 20: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

   Table S13. Cartesian coordinates of La species with 4 carbonate ligands.  

LaCar4_0bi4mo La -0.000516 0.001711 -0.001189 C -2.737083 1.587003 -1.917339 O -1.717417 0.996100 -1.249069 O 1.014107 1.723451 1.224435 C 1.618883 2.713283 1.924308 O 2.162596 3.678652 1.270950

O -0.978470 -1.690898 1.292244 C -1.569258 -2.706786 1.966980 O -1.551502 -2.679002 3.253318 O -3.680217 2.133616 -1.235314 O -2.714918 1.575127 -3.203709 O 1.621441 2.643984 3.208423

O -2.119970 -3.651754 1.291322 C 2.688305 -1.598709 -1.970501 O 3.640823 -2.143159 -1.300148 O 2.645081 -1.595303 -3.256530 O 1.681485 -0.999096 -1.290039

LaCar4_1bi3mo

La -0.000135 -0.076341 0.105193 C 0.002912 3.644753 0.423309 O 0.004810 4.372127 -0.642357 O 0.002402 4.155648 1.609172 O 0.001420 2.303856 0.292373 O -0.000049 -0.498080 2.586750 C -0.001413 -1.820751 2.562614 O -0.002239 -2.354237 1.366980 C -3.222823 -0.842133 -1.590620 O 2.037951 -0.540895 -1.023739 C 3.221589 -0.846695 -1.590434 O 4.298727 -0.698075 -0.896665 O 3.233927 -1.276664 -2.807264 O -0.001873 -2.519166 3.639884 O -3.235596 -1.273526 -2.806954 O -4.299863 -0.691092 -0.897224 O -2.038853 -0.537343 -1.024106

LaCar4_2bi2mo

La 0.000001 -0.160829 0.000000 C 2.817815 2.179798 -0.873384 C 1.306908 -2.035161 2.001710 C -2.817850 2.179759 0.873376 C -1.306871 -2.035192 -2.001702 O 3.181985 2.281684 -2.111987 O 1.792504 1.375861 -0.558116 O 3.416819 2.834123 0.069155 O 1.810255 -2.834708 2.878354

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 21: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

O 1.650518 -2.063747 0.739309 O 0.403442 -1.128607 2.323814 O -3.182003 2.281678 2.111981 O -1.792549 1.375807 0.558115 O -3.416868 2.834056 -0.069173 O -1.810208 -2.834747 -2.878344 O -1.650479 -2.063779 -0.739301 O -0.403427 -1.128617 -2.323812

LaCar4_3bi1mo

La 0.129567 0.000093 -0.047544 C 0.360783 2.791950 -1.344692 C 2.571382 0.001500 1.797404 C -3.534530 -0.003657 0.987575 C 0.367471 -2.789979 -1.345563 O 0.494164 3.936170 -1.937119 O 0.238037 2.682321 -0.048804 O 0.343035 1.662273 -2.020518 O 3.589399 0.001790 2.596200 O 2.705320 0.001737 0.494378 O 1.335954 0.000768 2.246735 O 0.503830 -3.933944 -1.937628 O 0.351300 -1.660202 -2.021205 O 0.239945 -2.680551 -0.050048 O -3.829551 -0.001028 2.252554 O -4.464190 -0.007738 0.080773 O -2.254234 -0.002123 0.612388

LaCar4_4bi0mo

La 0.000129 0.000048 -0.000078 C -0.860512 2.705671 1.298532 C -2.706065 -0.860585 -1.298130 C 2.705597 0.860430 -1.298730 C 0.860755 -2.705600 1.298421 O -1.214694 3.819488 1.869597 O -0.524606 1.648749 1.998381 O -0.818600 2.574546 -0.001613 O -3.820172 -1.215100 -1.868493 O -2.574293 -0.818486 0.001936 O -1.649632 -0.524602 -1.998580 O 3.819696 1.215096 -1.868894 O 1.649023 0.524946 -1.999210 O 2.573870 0.817685 0.001398 O 1.215275 -3.819491 1.869124 O 0.817819 -2.574425 -0.001700 O 0.525566 -1.648688 1.998542

           

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 22: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

   Table S14. Cartesian coordinates of Lu species with 3 carbonate ligands.  

LuCar3_0bi3mo Lu -0.001930 -0.000284 -0.004052

C 1.651621 2.986134 0.003740 O 0.976815 1.769458 -0.013888 O -2.023685 -0.040078 0.000987 C -3.414778 -0.067458 0.004455 O -3.968437 -0.083533 1.141734 O 1.038031 -1.734357 -0.032766 C 1.768606 -2.917582 0.004129 O 2.070188 -3.422027 -1.116047 O 1.926123 3.487275 -1.124895 O 1.916811 3.458692 1.146775

O -3.974449 -0.073021 -1.130045 O 2.051643 -3.360710 1.154862

 LuCar3_1bi2mo

Lu 0.000013 0.137072 -0.000071 C 2.978452 -1.550138 0.000150 O 3.479734 -1.820360 -1.134287 O 3.478095 -1.821094 1.135109 O 1.764282 -0.891236 -0.000516 O -0.000642 2.038013 1.115016 C -0.001279 2.774464 0.000041 O -0.001109 2.038204 -1.115014 O -1.763191 -0.892883 0.000409 C -2.977304 -1.551947 -0.000006 O -3.478388 -1.822100 1.134502 O -3.476986 -1.823190 -1.134891 O -0.001813 4.023851 0.000166

 LuCar3_2bi1mo

Lu 0.156156 -0.000009 -0.000177 C -3.273410 -0.000620 0.000088 C 1.448960 -2.349499 0.000136 C 1.447890 2.350143 0.000312

O -3.850131 -0.000918 1.134521 O -1.898956 -0.000944 -0.001477 O -3.852677 -0.000018 -1.133054 O 2.064505 -3.444802 -0.000029 O 1.092634 -1.709672 1.111023 O 1.093723 -1.708827 -1.110657 O 2.062824 3.445759 0.000397 O 1.092531 1.709719 -1.110664 O 1.092080 1.709764 1.111107

 LuCar3_3bi0mo

Lu -0.000078 -0.000073 -0.000304 C 1.908346 -1.927427 0.000378

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 23: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

C 0.715519 2.616212 0.000161 C -2.623655 -0.688536 0.000203 O 2.796554 -2.824036 0.000465 O 1.184344 -1.618906 -1.067994 O 1.606455 -1.200415 1.068503 O 1.048386 3.833488 0.000576 O 0.236100 1.991281 1.068208 O 0.810330 1.834896 -1.068159 O -3.844336 -1.008925 0.000479 O -1.843038 -0.790603 1.068360 O -1.994263 -0.216320 -1.068298

                                                                                 

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 24: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

   Table S15. Cartesian coordinates of Lu species with 4 carbonate ligands.  

LuCar4_0bi4mo Lu 0.000082 0.001010 -0.001717 C -2.625237 1.369378 -1.834030 O -1.583798 0.823944 -1.167803 O 0.842602 1.592058 1.140685 C 1.385798 2.632549 1.810298 O 1.903195 3.594595 1.132079

O -0.835284 -1.571674 1.171906 C -1.387737 -2.608409 1.839732 O -1.391714 -2.576913 3.126040 O -3.578970 1.898023 -1.153166 O -2.617003 1.333938 -3.120199 O 1.360571 2.614600 3.096339

O -1.884820 -3.579897 1.160293 C 2.627046 -1.395028 -1.811507 O 3.580095 -1.913951 -1.121544 O 2.620729 -1.380773 -3.097915 O 1.583764 -0.841781 -1.154845

 LuCar4_1bi3mo

Lu -0.000711 -0.074706 0.099650 C 0.023605 3.424926 0.445484 O 0.026493 4.177685 -0.603522 O 0.029834 3.913107 1.641900 O 0.013676 2.092305 0.285759

O -0.006575 -0.460505 2.361905 C -0.014010 -1.784515 2.311559 O -0.014723 -2.274211 1.101657 C -3.050312 -0.721827 -1.493363 O 1.856506 -0.466127 -0.932989 C 3.042268 -0.758718 -1.491072 O 4.110007 -0.655733 -0.773830 O 3.073159 -1.132065 -2.726556 O -0.019852 -2.507580 3.372479 O -3.086050 -1.098115 -2.727866 O -4.116451 -0.604028 -0.776147 O -1.860879 -0.441614 -0.936640

 LuCar4_2bi2mo

Lu -0.000022 -0.150943 0.000002 C 2.632697 2.063162 -0.833902 C 1.297667 -1.897545 1.786799 C -2.632571 2.063416 0.833723

C -1.297747 -1.897776 -1.786599 O 2.964453 2.189840 -2.080272 O 1.614504 1.263355 -0.506441 O 3.264772 2.696097 0.103152 O 1.832719 -2.696767 2.646122

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 25: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

O 1.570911 -1.932778 0.510446 O 0.422300 -0.974214 2.138004 O -2.963960 2.190121 2.080175 O -1.614581 1.263493 0.505912 O -3.264783 2.696498 -0.103155 O -1.832838 -2.697098 -2.645812 O -1.571055 -1.932780 -0.510251 O -0.422285 -0.974589 -2.137916

 LuCar4_3bi1mo

Lu 0.123192 0.000045 -0.052615 C 0.289875 2.635065 -1.171953 C 2.457377 -0.000120 1.553795 C -3.313989 -0.000496 0.920848 C 0.289928 -2.634756 -1.172266 O 0.401769 3.795857 -1.740641 O 0.231336 2.479665 0.120484 O 0.229456 1.521244 -1.868854 O 3.515719 -0.000012 2.302236 O 2.520723 0.000050 0.245721 O 1.245202 -0.000108 2.052632 O 0.403150 -3.795375 -1.741016 O 0.230703 -1.520763 -1.869010 O 0.231159 -2.479503 0.120186 O -3.611744 -0.000157 2.185908 O -4.245539 -0.001198 0.014683 O -2.037654 0.000132 0.546812

 LuCar4_4bi0mo

Lu -0.000070 -0.000094 -0.000025 C 1.922144 1.850768 1.125516

C -1.851275 1.923250 -1.125210 C 1.853473 -1.921325 -1.125060 C -1.924035 -1.852315 1.124770 O 2.781671 2.678205 1.650057 O 1.141859 1.099200 1.856454 O 1.780660 1.714396 -0.166320 O -2.677638 2.784409 -1.648822 O -1.710862 1.784107 0.166403 O -1.102887 1.140731 -1.857006 O 2.681543 -2.781047 -1.648339 O 1.098009 -1.145902 -1.857105 O 1.717881 -1.777096 0.166525 O -2.783783 -2.679809 1.649070 O -1.782129 -1.715743 -0.166869 O -1.143930 -1.100902 1.856156

         

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 26: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

Table S16. Second-order perturbative estimates of donor-acceptor interactions in the NBO basis

between carbonates and Ln(III). We specify the character of the acceptor orbital, while for the

donor it always correspond to oxygen lone pair. Only energies above 10 kcal mol-1 are reported.

donor acceptor Character of empty Ln orbital E(2) / kcal mol-1 [La(η1-CO3)2(η2-CO3)]3-

O8 (η2) La d (86%) 26.05 O6 (η2) La d (86%) 25.62 O5 (η1) La s (35%), d (34%), f (34%) 24.34 O9 (η1) La s (35%), d (34%), f (34%) 24.34 O5 (η1) La d (96%) 24.07 O9 (η1) La d (96%) 23.76 O9 (η1) La d (94%) 14.80 O5 (η1) La d (94%) 14.78 O9 (η1) La d (99%) 14.72 O5 (η1) La d (99%) 14.36

[Lu(η1-CO3)2(η2-CO3)]3- O9 (η1) Lu s (90%) 24.28 O5 (η1) Lu s (90%) 24.27 O8 (η2) Lu d (100%) 23.05 O6 (η2) Lu d (100%) 22.99 O5 (η1) Lu d (100%) 22.55 O9 (η1) Lu d (100%) 22.39 O5 (η1) Lu d (100%) 14.28 O9 (η1) Lu d (100%) 14.27 O5 (η1) Lu d (100%) 12.84 O9 (η1) Lu d (100%) 12.80 O9 (η1) Lu d (100%) 12.32 O5 (η1) Lu d (100%) 12.17 O6 (η2) Lu s (90%) 10.47 O8 (η2) Lu s (90%) 10.47

[La(η1-CO3)3(η2-CO3)]5- O6 (η2) La d (96%) 22.65 O5 (η1) La d (96%) 21.37 O10 (η1) La d (77%), f (22%) 16.64 O17 (η1) La d (77%), f (22%) 16.57 O10 (η1) La s (77%), f (23%) 16.28 O17 (η1) La s (77%), f (23%) 16.25 O8 (η2) La d (96%) 15.36 O17 (η1) La d (96%) 14.44 O10 (η1) La d (96%) 14.30 O8 (η2) La d (96%) 11.68 O5 (η1) La s (77%), f (23%) 11.47

[Lu(η1-CO3)3(η2-CO3)]5- O5 (η1) Lu d (84%) 36.35 O8 (η2) Lu d (84%) 25.96

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012

Page 27: Electronic Structure and Bonding of Lanthanoid(III) Carbonates. · 2012-08-01 · Electronic Structure and Bonding of Lanthanoid(III) Carbonates. Yannick Jeanvoine,a Pere Miró,b

O6 (η2) Lu s (52%), d (48%) 23.80 O10 (η1) Lu s (52%), d (48%) 19.34 O10 (η1) Lu d (69%), s (31%) 13.94 O10 (η1) Lu d (94%) 13.92 O17 (η1) Lu d (94%) 13.60 O5 (η1) Lu d (69%), s (31%) 13.22    Table S17. Relative energy obtained with different functionals with B3LYP optimized geometries (fixed) and optimizing the geometry with the given functional. Energies are in kcal/mol. B3LYP BLYP M05 M05-2X VSXC

LaC4 optimised fixeda optimised fixeda optimised fixeda optimised fixeda optimised 4m 0.00 0.00 0.00 0.00 0.00 0.00 0.00 7.10 8.03 3m1b 2.83 3.88 3.90 1.63 1.64 0.04 0.01 3.89 4.73 2m2b 6.93 8.95 8.98 4.50 4.53 1.45 1.36 1.26 1.32 1m3b 14.53 17.41 17.42 10.78 10.84 6.37 6.16 0.00 0.00 4b 23.86 27.41 27.40 18.75 18.82 13.54 13.21 0.77 1.39

LaC3 optimised fixeda optimised fixeda optimised fixeda optimised fixeda optimised

3m 43.82 37.90 37.85 45.99 46.07 54.69 54.74 54.27 54.12 2m1b 24.60 21.01 20.97 26.32 26.33 31.42 31.49 32.30 32.18 1m2b 10.22 8.58 8.57 11.20 11.20 13.51 13.54 14.38 14.27 3b 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 afixed to B3LYP geometry  

 

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2012